Conversion of hydrocarbon oils



Jan. 15 1946. G. s. DUNHAM CONVERSION OF HYDHOCARBON OILS Filed Aug, 8, 1941 65mg 221M007 INVENTOR TTORNEY Patented Jan. 15, 1946 UNITED STATES PATENT 0 FIFICE 3 Claims.

This application is a continuation-in-part of my prior flied application Serial No. 279,020, filed September 29, 1939.

This invention has to do with methods for the conversion of hydrocarbon oils utilizing vapor phase catalytic cracking in the presence of a clay like catalyst-in particle form which catalyst is regenerated in situ. r

The usual method of operating such processes contemplates preparing a charging stock of the nature or gas oil, no substantial portion of which boils above. about 700 F. at atmospheric pressure, super-heating such charge to about 850 F. and passing the heated vapors through a chamber containing a catalyst. The catalyst is principally composed oi hydrated aluminum silicates, in the form 0! pellets. particles or granules. In the catalyst chamber the vapors are cracked to yield gasoline, uncracked vapors, ands carbonaceous material or cake which is deposited upon the catalyst. The vapor eiiiuent iron the cracking is tractionated to separate gases, gasoline, and condensed uncracked gas oil. "I'he catalyst chamber is periodically withdrawn from operation, another one being substituted for continuity of operation. and the catalyst in the withdrawn chamber is regenerated in situ by burning oil the coke in a current or heated air. Such processes areiulivetplalnedinthevariousUnited States patents 01 Eugene Houdry and associates.

New, for any selected conversion rate, the amount or coke laid down upon the catalyst per unit volume of vapors charged to catalyst determinesnot only the length of run beiore regenerationisbutalsotheamountoi time which must be consumed in regeneration; time spent in regeneration is idle time irom the standpoint of cycle eiliciency; and the amountot coke .ao laid down increases quite rapidly withinereaaea in the percentage or charge to catalyst boiling above about 700 1".at atmospheric pressure. Consequently, every eflort'm made to preeonstituentshoiiingabove about 100 Rat atmospheric pressure. The usual method at performthepl'eparationisbyaubiectingthecharge toadhtillationandtractionationtoprepare achargevaporoipropcrendpcintwhiehis mheatedbetorepassingtotbe catalyst. Wherereduced crudeisutilisedtortheoriginali ing and vaporizing. it to separate therefrom charge materials at proper point, leaving the remainderas a heavy "viscous tar of little value. To avoid the production of large amounts oi tar itis advisable to heat the reduced sn de before vaporizationftofsuch a temperature that upon vaporization under proper conditions there is left unvaporizedra minimum amount of residue in the iorm' oifcoke, or in the form 01' a pitch or liquid asphaltthe'yield of which is the same or not greatly in excess oithe amount oi coke which would be; produced by coking distillation oi the reduced crude. It is also advisable to conduct such distillation with a minimum of crack il. to avoid iroprthe tar materials which are in the catalytic cracking charge boiling range but not desirable for such conversion. The desirable operation is one whichreduces'the crude charge to as little residue possible, while making every eilort to avoid cracking during such reduction. While the vapors fromsuch distillation contain a considerable amount of material too high in boiling point to be charged to thecatalyst', fractionation oi the vapors to remove this material yields a condensate oi considerably higher value than the tar iormerly produced. The process still does not permit tullutilisation oi the .origlnal crude for invention has ipr h eublect the provision on whe were ti -Tea minimum residue from areduced. crude charge oil, the enremainder of the oil is converted into materials suitable for charge to a catalytic vapor phase process. As a corollary obiect it provides for the production or yield of catalytically cracked gasoline from. a given amount or crude charge oil. it provides a process of such freeman mate-ital sublected to said cata- 0 a considerablydeupon the catalyst such cracking. In its broadest aspect, it has for oblect the provision of a'combin'ed process ior preparation and prees treatment oi charging stock and oi catalytic crachng, each so'amociated with the other as to provide a flexibility with regard to natureoiorisinalcharslnustockcombinedwitha minimum. variation in the operation and nature 80 of p oductsoithe catalytic cracking.

To more. readily understand this invention, reference to the drawing'attached to this single figure oi which shows in ticjiorin the apparatus and process I6 w r ppropria e t my pr ss.

In the drawing. reduced crude charge. ireed oi iractions lighter than gas oil by preceding distillation operations. is iorced by pump I through pipeiandcoilsliniurnaceltobedischarged through pipe in admixture with superheated steam supplied by pipe Ii into coking vessel 1. 1n vessel I there is deposited a coke. pitch. or liquid asphalt. the removal oi which irom the system is indicated by pipe 1. Overhead vapors irom I pass through pipe 0 to iractionator i0. Prepared charge vapor, item which undesirable heavy material has been condensed and.- separatediniractionator i0 through pipe ii and coil ii in iurnaoe i3 toenter catalyst case it. wherein it is cracked as beiore explained. Passingiromcase ll throughpipe ILtheeracked vapors enter iractionator it to be separated into uncracked product which departs through pipe i1 and cracked products which pass through pipe I! and condenser i! to separator 20 irom which non-con gases are withdrawn at Ii and cracked product at 22. while only one catalyst case ii is shown. it is understood that there are a sumcient number-oi catalyst bodies, so maniiolded. that vapors may be sent to another catalyst body when any one body is withdrawn from the circuit ior regeneration.

Returning to iractionator ii, the heavy material boiling irom 700' l". and upwards at atmospheric pressure which was separated therein is removed at pipe 28. This heavy condensate I collect in accumulator 2 and torso by means oi pump "and pipe I through coil 2! situated in i'urnace i. where the heavymaterial is viscosity broken. that is, subjected to a mild cracking suillcient to convert a male: portion oi the material boiling above 700' F. to material oi gas oil nature boiling below 700 1 The material so treated then to separator vessel I where vapor separation takes place in company with theincomingmaterial irompipelandthesuperheated steam irom pipe 0. This vaporization oithestreamiromviscositybreakercoilil not only separates that material into vapor and a product corresponding in nature to the minimum residue oi coke. pitch, or asphalt being simultaneously separated out oi the stream irom coil tandpipetbutitalsoineiiectinga more complete separation oi the material irom pipe I. Thisisbecaweoithspresenceinseparatorloianamountoiysporsboilingbelow 100' E, due entirely to the viscosity breaking operatiomiarinexcessoithatproportlonoisuch vapors arising iron the normal operation in coili. Thesevaporsassistingettingamore complete separation oi the minimum residue iromthechargeoilbypermittlngvaporisation toalowerpercentagebottomsioragiventemperature. Thepresenceoithesevaporsimmthe viscosity breaking operation. as well as the superheated steam irom pipe 0. permits oi carryingthedistillationoithereducedcrudetoa desired'minlmum residue. without cracking in.

coiltattemperaturesiorcoillesitwhichare iarbelowthosewhichwouldbeior such distillationtosimilarminimum residuein theabsenceoithecarryingpoweroithessadded materials. Asiswelltnowninthearhdistiihtiontocokeoraeimilarminimumresiduainthe absence oi such carrying materials. involves timesandtemp r tures givingrisetoiairly extlnsivecrsckingoithematerialtreatemw'hioh may be wholly avoided. with production oi residues similar in amount, by the method here shown.

The vaporous products oi viscosity breaking. both those newLv iormed products boiling below about 700 F. and those yet boiling above that range. pass into iractionator i0 and are therein ireed irom products undesirable ior catalytic cracking because oi high boiling point. The suitable vapors remain in the main vapor stream oi the process, while the high boiling material returns to coil 21 ior retreatment. In this manner, the whole oi the reduced crude charge becomes converted into charge vapor ior catalyst and a minimum residue. This minimum residue, whether it he coke. pitch. or asphalt, represents only a tow percent oi the original charge. the yield being oi about the same order as would be the yield oi coke were the original charge subjected to a dry or coking distillation. Since the whole oi the remainder passes through the catalyst a greatly increased yield oi catalytically cracked product is gotten over those operations where a tar iraction is reiected irom the system.

While viscosity breaking in connection with thermal cracking operations is known, as are various methods oi reducing crude charging stock to a minimum residue. the methods devel oped therein are not capable oi direct transier to catalytic cracking, since. due to the iar greater tolerance oi thermal cracking methods ior coke iormed during conversion. the methods so developed have not been iorced to be capable oi producing a charging stock oi the highly cokeiree characteristics demanded by catalytic vapor phase cracking.

It is true that viscosity breaking operations have heretoiore been associated with catalytic cracking. as in U. 8. Patent 2,007,268 to Sheldon, but it i signii'ioant that there was no attempt made therein to reduce the crude charge stock beyond a tar roushiv the equivalent oi that produced by ordinary iractionation oi desirable charging stock from reduced crude. Indeed, it has been thought heretofore that it would not be practicable to accomplish complete separation oi a reduced crude charge into a material wholly acceptable as charge for catalytic vapor phase crackingandaminimumresidue notdiiierlng neatly in amount irom the coke ordinarily producedbycokingdistillationoiacrudeoithe same nature.

Mypmcesshereindisclosediscapablenotonly oi providing such a complete separation at reduced cnide charge into a minimum residue and products capable oi being catalytically converted in vapor phase without undue deposition oi coke, but also it avoids the production oianundueamountoithermailycrackedproductoigasolinebollingpoint. sincethermally crackedgasolineisnotoithehighoctane quality attained by catalytic product. this is quite desirable. Furthermyprocemsinceitincreases the relative concentration or vapors boiling below about I00 I. at the point where the minimum residue is separated. that is in vapor separator'ioithedrawing,maieriallyassistsinthe reduction oi the charge to the desired minimum residue.

In general, the temperature, time. and pressureconditionsintbeseveralphasesoimy processwillnotdiiiermaterlallyiromthoseaiready established ior similar s eps oi process. 'i'l'ietemperatureandtimeconditionsiorthe viscosity breaking should be adjusted, however, soastocoupleamaaimumproduotionoi-materislboilingbelsIsbcut'lOOi'Lwithaminimumproductionoimaterllloigalolineboilins assaoss In general. temperatures oi about 000' beusedattheexitoicoiilasa maalmumwhennocarryingmateriaisuchas steamandvaporsirom coil I1 arebeingused, this temperature being reduced, as is known in the art, proportionately to the carryin p wer or the vapors. etc., present to accomplish the desired distillation without substantial cracking in coil 3, temperatures oi about 000 I. coupled with suitable time, as is known in the art, will be used in the viscosity breaking coil, and temperatures oi the order oi 850 P. will be used in the catalytic cracking.

The term "minimum residue." where used herein. reiers to a residue, either coke, pitch. or liquid asphalt. which residue, in amount, is oi the order or that amount oi coke which would be iormed by a coking distillation of the reduced crude chantin stock.

I claim:

1. That method for preparing a charge stock for vapor phase catalytic cracking from a crude oil irom which constituents lighter than gas oil have been removed comprising heating such crude and vaporizing it in the presence of carrying vapors, the proportioning oi carrying vapors being such that all portions of the crude other than ,a minimum residue are vaporized without heating the crude to temperatures conducive to substantial cracking thereof, iractionating the vapors to condense thereirom portions too heavy ior catalytic cracking charge. subjecting the condensate so iormed to viscosity breaking in the absence of residual portions of the crude to convert a substantial portion thereof to material suitable for catalytic cracking charge while minimising production of gasoline in such viscosity breaking, vaporizing the exit stream from thisvlscositvbreakingincompany withthe exit stream from reduced crude distillation to provide a substantial portion of the carrying vapors therefor, discarding the residues produced by such cunbined vaporization from the system. and-passing the vapors s0 produced to the said iractionating step.

2. That method oi preparing charge material oi gas oil nature and having an end point not point. I. or more will substantially above about 700' 1".. suitable as charge torvaporphasecatalytiocrackingoperations to produce cracked gas line. comprisin heating a crude oil mm which materials lighter vaporizing the crude in the presence oi carryingvaporssuiiicientinamounttodistillit toa minimum residue which is withdrawn irom the system, iractionatlng the combined vapors to condense thereirom substantially all materials boiling above a 100 1'. endpoint, viscosity breakin the absence oi residual irom this viscosity breaking to provide a substantial portion of the carrying vapors tor the distillation of the heated reduced crude.

3. That method oi preparing and converting materialoigasoilnatureandhavin anend point not substantially above about 100 1"., suitable as charge for vapor phase catalytic cracking operations to produce cracked gasoline, comprising heatlna a crude oil irom which materials li hter than gas oil have been removed to a temperature insufliclent to bring about substantial cracking or the heaviest portions thereof and vaporizing the crude in the presence or carrying vapors suiiicient in amount to distill it to a minimum residue which is withdrawn irom the system. iractionaiing the combined vapors to condense thareirom substantially all materials boiling above a 700' I". endpoint, viscosity breaking such condensate in the absence of residual portions oi the crude under conditions suitable for a maximum conversion thereof to materials boiling under 100' 1". while minimising conversion to gasoline. utilising the exit stream, superheating the overhead vapors from the iractionating operation to a temperature in excess of about 000' l". and passing them through a contact mass capable oi catalysing vapor phase crackingtoproduceasubetantiaiyieidorgasoline therefrom.

GIORBI 8. DURHAM.

CERTIFICATE CF CORRECTION Patent No. 2,393,028-

Jsnnary 15, 1911.6.

GEORGE S DUIIHAH,

it is hereby certified inst error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1. first column, line 2, for "Serial No. 279,020" read --Seri.al No. 29?,020"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

gned and sealed this 9121 day or April, a. 0. 191m.

(Seal) Leslie Frazer First Assistant Cuninissioner. of Patents.

assaoss In general. temperatures oi about 000' beusedattheexitoicoiilasa maalmumwhennocarryingmateriaisuchas steamandvaporsirom coil I1 arebeingused, this temperature being reduced, as is known in the art, proportionately to the carryin p wer or the vapors. etc., present to accomplish the desired distillation without substantial cracking in coil 3, temperatures oi about 000 I. coupled with suitable time, as is known in the art, will be used in the viscosity breaking coil, and temperatures oi the order oi 850 P. will be used in the catalytic cracking.

The term "minimum residue." where used herein. reiers to a residue, either coke, pitch. or liquid asphalt. which residue, in amount, is oi the order or that amount oi coke which would be iormed by a coking distillation of the reduced crude chantin stock.

I claim:

1. That method for preparing a charge stock for vapor phase catalytic cracking from a crude oil irom which constituents lighter than gas oil have been removed comprising heating such crude and vaporizing it in the presence of carrying vapors, the proportioning oi carrying vapors being such that all portions of the crude other than ,a minimum residue are vaporized without heating the crude to temperatures conducive to substantial cracking thereof, iractionating the vapors to condense thereirom portions too heavy ior catalytic cracking charge. subjecting the condensate so iormed to viscosity breaking in the absence of residual portions of the crude to convert a substantial portion thereof to material suitable for catalytic cracking charge while minimising production of gasoline in such viscosity breaking, vaporizing the exit stream from thisvlscositvbreakingincompany withthe exit stream from reduced crude distillation to provide a substantial portion of the carrying vapors therefor, discarding the residues produced by such cunbined vaporization from the system. and-passing the vapors s0 produced to the said iractionating step.

2. That method oi preparing charge material oi gas oil nature and having an end point not point. I. or more will substantially above about 700' 1".. suitable as charge torvaporphasecatalytiocrackingoperations to produce cracked gas line. comprisin heating a crude oil mm which materials lighter vaporizing the crude in the presence oi carryingvaporssuiiicientinamounttodistillit toa minimum residue which is withdrawn irom the system, iractionatlng the combined vapors to condense thereirom substantially all materials boiling above a 100 1'. endpoint, viscosity breakin the absence oi residual irom this viscosity breaking to provide a substantial portion of the carrying vapors tor the distillation of the heated reduced crude.

3. That method oi preparing and converting materialoigasoilnatureandhavin anend point not substantially above about 100 1"., suitable as charge for vapor phase catalytic cracking operations to produce cracked gasoline, comprising heatlna a crude oil irom which materials li hter than gas oil have been removed to a temperature insufliclent to bring about substantial cracking or the heaviest portions thereof and vaporizing the crude in the presence or carrying vapors suiiicient in amount to distill it to a minimum residue which is withdrawn irom the system. iractionaiing the combined vapors to condense thareirom substantially all materials boiling above a 700' I". endpoint, viscosity breaking such condensate in the absence of residual portions oi the crude under conditions suitable for a maximum conversion thereof to materials boiling under 100' 1". while minimising conversion to gasoline. utilising the exit stream, superheating the overhead vapors from the iractionating operation to a temperature in excess of about 000' l". and passing them through a contact mass capable oi catalysing vapor phase crackingtoproduceasubetantiaiyieidorgasoline therefrom.

GIORBI 8. DURHAM.

CERTIFICATE CF CORRECTION Patent No. 2,393,028-

Jsnnary 15, 1911.6.

GEORGE S DUIIHAH,

it is hereby certified inst error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1. first column, line 2, for "Serial No. 279,020" read --Seri.al No. 29?,020"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

gn d nd sealed this 9th day of April, a. 0. late.

(Seal) Leslie Frazer First Assistant Cuninissioner. of Patents. 

